Homosubstituted amido‐functionalized polyoctahedral oligomeric silsesquioxanes (POSS) have been synthesized by using acyl chlorides in high yields (ca. 95 %). The method proved to be superior over “conventional” syntheses applying carboxylic acids or acid anhydrides, which are much less efficient (ca. 60 % yield). A palette of aryl and alkyl groups has been used as side‐chains. The structures of the resulting amide‐POSS are supported by multinuclear 1H, 13C, 29Si NMR and FTIR spectroscopy and their full conversion into octasubstituted derivatives was confirmed using mass spectrometry. We also demonstrate that the functionalized silsesquioxanes with bulky organic side‐chains attached to cubic siloxane core form spherical‐like, well‐separated nanoparticles with a size of approximately 5 nm. 相似文献
Films of poly (methyl methacrylate) (PMMA) were prepared by the addition of photoinitiator to the polymer. The influence of five organic photoinitiators on thermal stability of poly(methyl methacrylate) was studied by thermogravimetric analysis. Next, the PMMA films doped with these photoinitiators were UV irradiated and investigated in terms of changes in their thermal stability. It was found that the photoinitiators had accelerated thermal degradation of non-irradiated PMMA films due to the action of free radicals coming from the additives’ thermolysis. For UV-irradiated specimens, the effect of photoinitiator on PMMA thermal stability depended on the chemical structure of organic compound modifying the polymer. In general, thermal stability of irradiated samples was higher in the presence of additives. Thermal destruction of modified PMMA can be explained by the formation of resonance structures in aromatic photoinitiators and consumption of energy in dissipation processes. 相似文献
Tyrosinase/laccase bienzyme biosensor for amperometric determination of phenolic compounds was constructed. Enzymes were immobilized in titania gel matrix. The obtained biosensor was successfully used for determination of 2,6-dimethoxyphenol, 4-tertbutylcatechol, 4-methylcatechol, 3-chlorophenol and catechol. The highest sensitivity and the widest linear range were noticed for catechol, 234 mA L mol− 1 and 2.0 × 10− 7–3.2 × 10− 5 mol/L, respectively. Detection limit for catechol, at signal-to-noise ratio of 3 was 1.3 × 10− 7 mol/L. 相似文献
A theory of cationic dimeric (gemini) surfactant adsorption onto negatively charged surface is presented. In the proposed model it is assumed that the adsorbed phase is a mixture of singly dispersed molecules of surfactant and spherical, globular and cylindrical aggregates of different dimensions. Only the “excluded area” interactions between the adsorbed species are considered and the effects of surface heterogeneity on monomer adsorption are taken into account. The aggregation behavior of gemini surfactants is based on the additive free energy model proposed by Camesano and Nagarajan (2000). The calculated surfactant adsorption isotherms and the differential molar enthalpies of micellisation and adsorption are compared with the experimental results obtained for a series of gemini surfactants depending on the length of a spacer, temperature or the presence of electrolyte. On the basis of theoretical results the evolution of adsorbed phase of gemini surfactants with the increasing adsorption is discussed. It is shown that the evaluated cmc values and the dimensions of surfactant aggregates are in a good agreement with experiment. Unfortunately, the theoretical model does not describe properly the temperature dependence of micellisation process. 相似文献
Reactions of Ti(OiPr)4 or Zr(OEt)4 with 4 equivalents of 2,3-dihydro-2,2-dimethyl-7-benzofuranol (ddbfoH) in toluene gave neutral complexes that in the solid state are dimers of [Ti(micro-ddbfo)2(ddbfo)6] and [Zr(ddbfo)3(EtOH)(micro-EtO)]2 composition. The former could also be conveniently synthesized in a direct reaction of TiCl4 with ddbfoH. This air-stable aryloxo compound was found to initiate living ring-opening polymerization of lactides affording polyesters with narrow molecular weight distribution. It also catalyzed addition of terminal acetylenes to aryl aldehydes. 相似文献
A new vasopressin analogue, [His(1,6)]AVP, was synthesized and characterized by potentiometric measurements as well as by UV-Vis, CD and EPR spectroscopy. At the physiological pH the peptide forms a stable complex with Cu(2+) ions which is characterized by the {NH(2), N(Im), N(Im(macrochelate))} binding mode. The replacement of both Cys by His residues in the vasopressin sequence results in a very significant increase in the efficiency of Cu(2+) binding. 相似文献
The Zn-Ni+Ni coatings were deposited under galvanostatic conditions at the current density range from 20 to 60 mA cm?2. The influence of deposition current density on surface morphology, chemical and phase composition and corrosion resistance of obtained coatings, was investigated. Structural investigations were conducted by X-ray diffraction method. Surface morphology and surface chemical composition of the obtained coatings were determined by a scanning electron microscope. Studies of electrochemical corrosion resistance were carried out in the 5% NaCl solution, using potentiodynamic and Scanning Kelvin Probe (SKP) methods. A possibility of incorporation of nickel powder from a suspension bath to the Zn-Ni matrix, during galvanostatic deposition was demonstrated. The results of chemical composition analysis show that the Zn-Ni + Ni coatings contain approximately 15?C18% at Ni. It was found that surface morphology, surface chemical and phase composition of Zn-Ni + Ni coatings depend in small degree on deposition current density. However, the current density influences distribution of nickel powder on the surface of these coatings. The optimal values of current density on account of corrosion resistance, are found to be j = 40?C50 mA cm?2. 相似文献
The fundamental nature of reactivity in cytochrome P450 enzymes is currently controversial. Modelling of bacterial P450cam has suggested an important role for the haem propionates in the catalysis, though this finding has been questioned. Understanding the mechanisms of this enzyme family is important both in terms of basic biochemistry and potentially in the prediction of drug metabolism. We have modelled the hydroxylation of camphor by P450cam, using combined quantum mechanics/molecular mechanics (QM/MM) methods. A set of reaction pathways in the enzyme was determined. We were able to pinpoint the source of the discrepancies in the previous results. We show that when a correct ionization state is assigned to Asp297, no spin density appears on the haem propionates and the protein structure in this region remains preserved. These results indicate that the haem propionates are not involved in catalysis. 相似文献
Triple duty : A synthetic molecular clip traps nicotinamide adenine dinucleotide phosphate (NADP+; see picture) as well as occupying both the cofactor‐ and the substrate‐binding site in glucose‐6‐phosphate (G6P) dehydrogenase. This combination of two inhibition mechanisms makes the clip highly effective and selective for this enzyme over other dehydrogenases.